Process for preparing rigid and flexible polyurethane foams

ABSTRACT

Process for preparing a rigid and a flexible polyurethane foam by reacting a polyisocyanate and two different polyols under foam forming conditions, the polyisocyanate being reacted with said polyols in the absence of compounds comprising primary, secondary or tertiary amines. Flexible foams are obtained which do not show a major glass transition temperature between −100° C. and +25° C.

This is a division of application Ser. No. 08/963,744, filed Nov. 4,1997 which is now U.S. Pat. No. 6,147,134.

The present invention is concerned with a process to prepare rigid andflexible polyurethane foams.

Conventional flexible polyurethane foams are widely known. Such foamsshow a relatively high resilience (ball rebound), a relatively lowmodulus, a relatively high sag factor and a relatively low hysteresisloss. Such foams further show a major glass-rubber transition belowambient temperature, generally in the temperature range of −100° C. to−10° C. The commonly applied relatively high molecular weight polyetherand polyester polyols in such foams are responsible for the sub-ambientglass transition temperature (Tg^(s)) These polyether and polyesterpolyols are often referred to as soft segments. Above Tg^(s) the foamdisplays its typical flexible properties until softening and/or meltingof the isocyanate-derived urethane/urea clusters (“hard domains”) takesplace. This softening and/or melting temperature (Tg^(h) and /or Tm^(h))often coincides with the onset of thermal degradation of polymersegments. The Tg^(h) and/or Tm^(h) for flexible polyurethane foams isgenerally higher than 100° C., often even exceeding 200° C. At theTg^(s) a sharp decrease of the modulus of the flexible foam is observed.Between Tg^(s) and Tg^(h)/Tm^(h) the modulus remains fairly constantwith increasing temperature and at Tg^(h)/Tm^(h) again a substantialdecrease of the modulus may take place. A way of expressing the presenceof Tg^(s) is to. determine the ratio of the Young's storage modulus E′at −100° C. and +25° C. as per Dynamic Mechanical Thermal Analysis (DMTAmeasured according to ISO/DIS 6721-5). For conventional flexiblepolyurethane foams the$\frac{E^{\prime} - {100{^\circ}\quad {C.}}}{E^{\prime} + {25{^\circ}\quad {C.}}}\quad {ratio}\quad {is}\quad {at}\quad {least}\quad 25.$

Another feature of Tg^(s) by DMTA (ISO/DIS 6721-5) is that forconventional flexible polyurethane foams the maximum value of the$\frac{{{Young}'}s\quad {loss}\quad {modulus}\quad E^{''}}{{{Young}'}s\quad {storage}\quad {modulus}\quad E^{\prime}}\left( \tan_{\delta \quad m\quad a\quad {x.}} \right)$

−100° C./+25° C. temperature range varies from 0.20-0.80 in general. TheYoung's loss modulus E″ is measured by DMTA (ISO/DIS 6721-5) as well.

Conventional flexible foams are made by reacting a polyisocyanate and arelatively high molecular weight isocyanate reactive polymer, often apolyester or polyether polyol, in the presence of a blowing agent andoptionally further using limited amounts of relatively low molecularweight chain extenders and cross-linkers and optionally using additiveslike catalysts, surfactants, fire retardants, stabilisers andantioxidants. The relatively high molecular weight isocyanate reactivepolymer in general represents the highest weight fraction of the foam.Such flexible foams may be prepared according to the one-shot, thequasi- or semi-prepolymer or the prepolymer process. Such flexible foamsmay be moulded foams or slabstock foams and may be used as cushioningmaterial in furniture and automotive seating and in mattresses, ascarpet backing, as hydrophilic foam in diapers and as packaging foam.Further they may be used for acoustic applications, e.g. soundinsulation. Examples of prior art for these conventional flexible foamsare EP-10850, EP-22617, EP- 11 121, EP-296449, EP-309217, EP-309218,EP-392788 and EP-442631.

Conventional rigid foams are made in a similar way with the proviso thatoften the polyisocyanates have a higher isocyanate functionality, theamount of high molecular weight polyols used is lower and the amount andfunctionality of the cross-linkers is higher.

WO92/12197 discloses an energy-absorbing, open-celled, water-blown,rigid polyurethane foam obtained by reacting a polyurethane foamformulation, comprising water which acts as a blowing agent and acell-opener, in a mould wherein the cured foam has a moulded density ofabout 32 to 72 kg/m³ and a crush strength which remains constant from 10to 70% deflection at loads of less than 70 psi. The foams have minimalspring back or hysteresis.

GB2096616 discloses a directionally flexibilized, rigid, closed-cellplastic foam. The rigid foams are flexibilized in order to use them fore.g. pipe-insulation. Cells should remain closed.

U.S. Pat. No. 4299883 discloses a sound-absorbent material made bycompressing a foam having closed cells to such an extent that the foamrecovers to 50-66% of its original thickness. By the compression thecells are ruptured and the foam becomes flexible and resilient; it mayreplace felt. The disclosure mainly refers to polycarbodiimide foams.

EP561216 discloses the preparation of foam boards having improved heatinsulation properties, wherein the foam has anisotropic cells having alength ratio of the long and the small axis of 1.2-1.6 and a density of15-45 kg/m³ and wherein the cells have been crushed in the direction ofthe plate thickness. The disclosure actually refers to polystyreneboards.

EP641635 discloses a process for preparing foam boards, having a dynamicstiffness of at most 10 MN/m³, by crushing a board of 17-30 kg/m³density at least twice to 60-90% of its original thickness. Preferablyclosed-celled polystyrene is used. In the examples it is shown that apolystyrene foam which has been crushed showed a better heat insulationthan an uncrushed one.

U.S. Pat. No. 4454248 discloses a process for preparing a rigidpolyurethane foam wherein a partially cured rigid foam is softened, thencrushed and re-expanded and fully cured.

In copending patent application PCT/EP9601594 a class of flexiblepolyurethane foams is described such foams having no major glass-rubbertransition between −100° C. and +25° C. In more quantitative terms thesefoams show a ratio E′⁻¹⁰⁰° C./E′₊₂₅° C. of 1.3 to 15.0, preferably of1.5 to 10 and most preferably of 1.5 to 7.5. The tan_(δmax) over the−100° C. to +25° C. temperature range is below 0.2. The core density ofsuch foams may range from 4-30 kg/m³ and preferably ranges from 4-20kg/m³ (measured according to ISO/DIS845). Such foams are made bycrushing a rigid foam.

The present invention is concerned with a process for preparing rigidpolyurethane foams by reacting a polyisocyanate (1), a polyether polyol(2) having a hydroxyl number of at least 150 mg KOH/g and an averagenominal hydroxyl functionality of from 2 to 8, a polyether polyol (3)having a hydroxyl number of from 10 to less than 150 mg KOH/g and anaverage nominal hydroxyl functionality of from 2 to 6 and water whereinthe amount of polyisocyanate (1), polyol (2), polyol (3) and water is55-80, 3-20, 10-30 and 2-6 parts by weight respectively per 100 parts byweight of polyisocyanate (1), polyol (2), polyol (3) and water andwherein the reaction is conducted at an isocyanate index of 102-200 andpreferably of 102-150 and wherein the polyisocyanate is reacted with oneor more isocyanate-reactive compositions comprising one or more of theaforementioned polyol (2), polyol (3) and water and not comprisingcompounds which have a primary, secondary or tertiary nitrogen atom.

The improved process gives foams with reduced thermal degradation,especially when such foams are made as large buns e.g. on a movingconveyor belt (slab-stock foam), the foams have improved stability and alower amount of extractables.

The present invention is more in particular concerned with a process forpreparing a rigid foam by reacting a polyisocyanate (1), a polyetherpolyol (2) having an average equivalent weight of 70-300 and preferablyof 70-150, having an average nominal hydroxyl functionality of from 2 to6 and preferably from 2 to 3 and oxyethylene content of at least 75% byweight, a polyether polyol (3) having an average equivalent weight of1000-3000, having an average nominal hydroxyl functionality of 2 to 3and preferably of 2 and having the structure

HO—(EO)_(X)—(PO)_(Z)—(EO)_(Y)—X[-0-(EO)_(Y)—(PO)_(Z)—(EO)_(X)H]_(n)  Formula1

wherein EO is an ethylene oxide radical, PO is a propylene oxideradical, x=1-15 and preferably 3-10, y=0-6 and preferably 1-4, z is suchso as to arrive at the above equivalent weight, n=1-2 and X is ahydrocarbon radical having 2-10 and preferably 2-6 carbon atoms or aradical having the formula —CH₂—CH₂—(OCH₂—CH₂)₁₋₂—, and water whereinthe amount of polyisocyanate (1), polyol (2), polyol (3) and water is55-80, 3-20, 10-30 and 2-6 parts by weight respectively per 100 parts byweight of polyisocyanate (1), polyol (2), polyol (3) and water andwherein the reaction is conducted at an isocyanate index of 102-200 andpreferably of 102-150 and wherein the polyisocyanate is reacted with oneor more isocyanate-reactive compositions comprising one or more of theaforementioned polyol (2), polyol (3) and water and not comprisingcompounds which have a primary, secondary or tertiary nitrogen atom.

Preferably the amount of water is 3-5 parts by weight calculated on thesame basis as above. Preferably the weight ratio of water and polyol (3)is 0.1 to 0.4:1 and the weight ratio of polyol (3) and of polyol (2)+water is 0.9-2.5:1. The core density of the rigid foams obtained ispreferably 3-15 kg/M³ (ISO 845).

Further the present invention is concerned with the rigid foams soobtainable, with a process for preparing a flexible foam by crushing arigid foam so obtained, with flexible foams so obtainable, with reactionsystems comprising the ingredients for making these foams and withpolyol compositions comprising the aforementioned polyether polyol (2),polyether polyol (3) and water in an amount of 15-40,45-75 and 5-20parts by weight respectively per 100 parts by weight of polyol (2),polyol (3) and water with the proviso that the composition does notcomprise compounds having primary, secondary or tertiary nitrogen atoms.Still further the present invention is concerned with a compositioncomprising polyol (2), water and a phosphate, the amount of polyol (2)and water being 45-80 and 20-55 parts by weight respectively per 100parts by weight of polyol (2) and water, the amount of phosphate being0.025 to 2.5% by weight calculated on the amount of polyol (2) and waterwith the proviso that the composition does not comprise compounds havingprimary, secondary or tertiary nitrogen atoms.

The foams according to the present invention have no major glass-rubbertransition between −100° C. and +25° C. In more quantitative terms thesefoams show a ratio E′⁻¹⁰⁰° C./E′_(+25° C.) of 1.3 to 15.0, preferably1.5 to 10 and most preferably of 1.5 to 7.5. The core density of theflexible foams preferably is 3-20 kg/m³ (ISO 845).

In the context of the present application a flexible polyurethane foamis a crushed foam having a ball rebound (measured according to ISO 8307)of at least 40%, preferably at least 50% and most preferably 55-85% inat least one of the three dimensional directions and a sag factor (CLD65/25) of at least 2.0 (measured according to ISO 3386/1). Preferablysuch flexible foams have a Young's storage modulus at 25° C. of at most500 kPa, more preferably at most 350 kPa and most preferably between 10and 200 kPa (Young's storage modulus measured by DMTA according toISO/DIS 6721-5). Further, such flexible foams preferably have a sagfactor (CLD 65/25) of at least 3.5 and most preferably 4.5-10 (measuredaccording to ISO 3386/1). Still further such flexible foams preferablyhave a CLD hysteresis loss (ISO 3386/1) of below 55%, more preferablybelow 50% and most preferably below 45%.

In the context of the present patent application a rigid polyurethanefoam is an uncrushed foam having a ball rebound measured in thedirection of foam rise of less than 40% (ISO 8307 with the proviso thatno preflex conditioning is applied, that onlyone rebound value persample is measured and that test pieces are conditioned at 23° C.±2° C.and 50±5% relative humidity) and/or having a CLD 65/25 sag factormeasured in the direction of foam rise of less than 2.0 (ISO 3386/1 withthe proviso that the sag factor is determined after the firstload-unload cycle); these properties both being measured at a coredensity of the foam of 3-15 kg/m³. Preferably the ratio E′⁻¹⁰⁰°C./E′_(+25° C.) of such a rigid foam is 1.3-15. If in the presentapplication ISO 8307 and ISO 3386/1 are mentioned in relation to rigidfoams they refer to the tests as described above including the provisos.

The flexible polyurethane foams according to the present invention areprepared by reacting a polyisocyanate and a polyfunctionalisocyanate-reactive polymer under foam forming conditions to prepare arigid polyurethane foam and by crushing this rigid polyurethane foam.Further the present invention is concerned with the process forpreparing such rigid foams and with reaction systems comprising theingredients for making such foams.

In the context of the present invention the following terms have thefollowing meaning:

1) isocyanate index or NCO index or index:

the ratio of NCO-groups over isocyanate-reactive hydrogen atoms presentin a formulation, given as a percentage:$\frac{\lbrack{NCO}\rbrack \times 100}{\left\lbrack {{active}\quad {hydrogen}} \right\rbrack}\quad {(\%).}$

In other words the NCO-index expresses the percentage of isocyanateactually used in a formulation with respect to the amount of isocyanatetheoretically required for reacting with the amount ofisocyanate-reactive hydrogen used in a formulation.

It should be observed that the isocyanate index as used herein isconsidered from the point of view of the actual foaming processinvolving the isocyanate ingredient and the isocyanate-reactiveingredients. Any isocyanate groups consumed in a preliminary step toproduce modified polyisocyanates (including such isocyanate-derivativesreferred to in the art as quasi or semi-prepolymers and prepolymers) orany active hydrogens consumed in a preliminary step (e.g. reacted withisocyanate to produce modified polyols or polyamines) are not taken intoaccount in the calculation of the isocyanate index. Only the freeisocyanate groups and the free isocyanate-reactive hydrogens (includingthose of the water) present at the actual foaming stage are taken intoaccount.

2) The expression “isocyanate-reactive hydrogen atoms” as used hereinfor the purpose of calculating the isocyanate index refers to the totalof active hydrogen atoms in hydroxyl groups present in the reactivecompositions; this means that for the purpose of calculating theisocyanate index at the actual foaming process one hydroxyl group isconsidered to comprise one reactive hydrogen and one water molecule isconsidered to comprise two active hydrogens.

3) Reaction system a combination of components wherein thepolyisocyanates are kept in one or more containers separate from theisocyanate-reactive components.

4) The expression “polyurethane foam” as used herein refers to cellularproducts as obtained by reacting polyisocyanates withisocyanate-reactive hydrogen containing compounds, using foaming agents,and in particular includes cellular products obtained with water asreactive foaming agent (involving a reaction of water with isocyanategroups yielding urea linkages and carbon dioxide and producingpolyurea-urethane foams) and with polyols as isocyanate-reactivecompounds.

5) The term “average nominal hydroxyl functionality” is used herein toindicate the number average functionality (number of hydroxyl groups permolecule) of the polyol or polyol composition on the assumption thatthis is the number average functionality (number of active hydrogenatoms per molecule) of the initiator(s) used in their preparationalthough in practice it will often be somewhat less because of someterminal unsaturation.

6) The word “average” refers to number average unless indicatedotherwise.

Suitable organic polyisocyanates for use in the process of the presentinvention include any of those known in the art for the preparation ofrigid polyurethane foams, like aliphatic, cycloaliphatic, araliphaticand, preferably, aromatic polyisocyanates, such as toluene diisocyanatein the form of its 2,4 and 2,6-isomers and mixtures thereof anddiphenylmethane diisocyanate in the form of its 2,4′-, 2,2′- and4,4′-isomers and mixtures thereof, the mixtures of diphenylmethanediisocyanates (MDI) and oligomers thereof having an isocyanatefunctionality greater than 2 known in the art as “crude” or polymericMDI (polymethylene polyphenylene polyisocyanates), the known variants ofMDI comprising urethane, allophanate, urea, biuret, carbodiimide,uretonimine and/or isocyanurate groups.

Mixtures of toluene diisocyanate and diphenylmethane diisocyanate and/orpolymethylene polyphenylene polyisocyanates may be used. Most preferablypolyisocyanates are used which have an average isocyanate functionalityof 2.1-3.0 and preferably of 2.2-2.8.

Preferably MDI, crude or polymeric MDI and/or liquid variants thereofare used said variants being obtained by introducing uretonimine and/orcarbodiimide groups in said polyisocyanates, such a uretonimine and/orcarbodiimide modified polyisocyanate having an NCO value of at least 20%by weight, and/or by reacting such a polyisocyanate with one or morepolyols having a hydroxyl functionality of 2-6 and a molecular weight of62-500 so as to obtain a modified polyisocyanate having an NCO value ofat least 20% by weight.

Suitable polyether polyols (2) have been fully described in the priorart and include reaction products of alkylene oxides, for exampleethylene oxide and/or propylene oxide, with initiators containing from 2to 8 active hydrogen atoms per molecule and noprimary, secondary ortertiary nitrogen atoms. Suitable initiators include: polyols, forexample ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, butane diol, glycerol,trimethylolpropane, pentaerythritol, sorbitol and sucrose and mixturesof such initiators. Other suitable polyether polyols (2) includeethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, butane diol, glycerol, trimethylolpropane and the otherinitiators mentioned before. Mixtures of such isocyanate-reactivecompounds may be used as well. Most preferred polyols (2) are thosehaving an average equivalent weight of 70-300 and preferably of 70-150,having an average nominal hydroxyl functionality of from 2 to 3 and anoxyethylene content of at least 75% by weight. Such a most preferredpolyol may contain a polyol having an equivalent weight below 70 whilemeeting the other criteria as to functionality and oxyethylene contentprovided the average equivalent weight remains in the 70-300 range. Suchmost preferred polyols are known as such and commercially available.

Polyether polyols (3) are generally known in the art and includereaction products of alkylene oxides, for example ethylene oxide and/orpropylene oxide, with initiators containing from 2 to 6 active hydrogenatoms per molecule and no primary, secondary or tertiary nitrogen atoms.Suitable initiators are ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, butane diol, glycerol,trimethylolpropane, pentaerythritol, sorbitol and mixtures of suchinitiators.

Most preferred polyether polyols (3) are those according to formula 1,described hereinbefore. Those having a nominal hydroxyl functionality of3 may be prepared by ethoxylation of an initiator, followed bypropoxylation and again ethoxylation, wherein the initiator is a triollike glycerol and/or trimethylol propane. Those having a nominalhydroxyl functionality of 2 may be prepared by ethoxylation of ethyleneglycol, diethylene glycol and/or triethylene glycol, followed bypropoxylation and again ethoxylation; or by propoxylation of ethyleneglycol, diethyleneglycol and/or triethylene glycol followed byethoxylation; or by propoxylation of a polyoxyethylene polyol having4-15 oxyethylene groups followed by ethoxylation. Mixtures of such mostpreferred polyols may be used as well. Although not necessary otherpolyols may be used together with these most preferred polyols accordingto formula 1, provided the amount does not exceed 30% by weight based onthe weight of these polyols according to formula 1. Such polyolsaccording to formula 1 are commercially available (e.g. Daltocel F 430from Imperial Chemical Industries PLC).

In order to prepare a foam water is used as a blowing agent. However ifthe amount of water is not sufficient to obtain the desired density ofthe foam any other known way to prepare polyurethane foams may beemployed additionally, like the use of reduced or variable pressure, theuse of a gas like air, N₂ and CO₂, the use of more conventional blowingagents like chlorofluorocarbons, hydrofluorocarbons, hydrocarbons andfluorocarbons, the use of other reactive blowing agents, i.e. agentswhich react with any of the ingredients in the reacting mixture and dueto this reaction liberate a gas which causes the mixture to foam and theuse of catalysts which enhance a reaction which leads to gas formationlike the use of carbodiimide-formation-enhancing catalysts such asphospholene oxides. Combinations of these ways to make foams may be usedas well. The amount of blowing agent may vary widely and primarilydepends on the desired density. Water may be used as liquid atbelow-ambient, ambient or elevated temperature and as steam. A preferredcombination of blowing agent is water and CO₂ wherein the CO₂ is addedto the ingredients for making the foam in the mixing head of a devicefor making the foam, to one of the isocyanate-reactive ingredients andpreferably to the polyisocyanate before the polyisocyanate is broughtinto contact with the isocyanate-reactive ingredients.

If a cyclic polyisocyanate and more in particular an aromaticpolyisocyanate and most in particular an MDI or polymethylenepolyphenylene polyisocyanate is used the content of cyclic and more inparticular of aromatic residues in the flexible foam is relatively highas compared to conventional flexible polyurethane foams. The foamsaccording to the invention preferably have a content of benzene rings,derived from aromatic polyisocyanates, which is 30 to 56 and mostpreferably 35 to 50% by weight based on the weight of the foam. Sincepolyols, polymer polyols, fire retardants, chain extenders and/orfillers which contain benzene rings may be used, the overall benzenering content of the flexible foam may be higher and preferably rangesfrom 30 to 70 and most preferably from 35 to 65% weight as measured bycalibrated Fourier Transform Infra Red Analysis.

In addition to the polyisocyanate, the isocyanate-reactive compounds andthe blowing agent, one or more auxiliaries or additives known per se forthe production of polyurethane foams may be used provided they do notcontain primary, secondary or tertiary nitrogen atoms. Such optionalauxiliaries or additives include foam-stabilizing agents or surfactants,for example siloxane-oxyalkylene copolymers and polyoxyethylenepolyoxypropylene block copolymers, urethane/urea catalysts, for exampletin compounds such as dibutyltin dilaurate and in particular stannousoctoate and/or phosphates like NaH₂PO₄ and Na₂HPO₄, and fire retardants,for example halogenated alkyl phosphates such as tris chloropropylphosphate, anti-oxidants like tertiary nonyl phenols, anti-staticagents, UV stabilisers, anti-microbial and anti-fungal compounds andfillers like latex, TPU, silicates, barium and calcium sulphates, chalkand glass fibers or beads.

It is preferred to use a catalyst enhancing the formation of urethaneand/or urea groups and in particular to use stannous octoate optionallytogether with other catalysts. The amount of catalyst may range from 0.1to 5 and preferably from 0.1 to 3% by weight calculated on the weight ofall ingredients used to make the foam; the amount of stannous octoatemay range from 0.1 to 3 and preferably 0.1 to 2% by weight calculated onthe same basis.

In operating the process for making rigid foams according to theinvention, the known one-shot, prepolymer or semi-prepolymer techniquesmay be used together with conventional mixing methods and the rigid foammay be produced in the form of slabstock, mouldings including foam infabric and pour-in-place applications, sprayed foam, frothed foam orlaminates with other materials such as hardboard, plasterboard,plastics, paper or metal or with other foam layers.

It is convenient in many applications to provide the components forpolyurethane production in pre-blended formulations based on each of theprimary polyisocyanate and isocyanate-reactive components. Inparticular, an isocyanate-reactive composition may be used whichcontains the auxiliaries, additives and the blowing agent in addition tothe isocyanate-reactive compounds (2) and (3) in the form of a solution,an emulsion or dispersion. The isocyanate-reactive components may alsobe supplied independently to the polyisocyanate as two or morecompositions containing the additives and auxiliaries; e.g. onecomposition comprising water and polyol (2) and another compositioncomprising polyol (3), catalyst and antioxidant may be fed fromdifferent storage tanks into the mixing head of a device for makingfoam, in which mixing head they are mixed with the polyisocyanate.

The rigid foam is prepared by allowing the aforementioned ingredients toreact and foam until the foam does not rise any more. After rise curingof the foam may be continued as long as desirable. In general a curingperiod of 1 minute to 24 hours and preferably of 5 minutes to 12 hourswill be sufficient. If desired curing may be conducted at elevatedtemperature. Subsequently the foam may be crushed. It is howeverpreferred to allow the rigid foam obtained to cool down to below 80° C.prior to crushing. The rigid foam (i.e. before crushing) preferably hasa core density of 3-15 kg/m³ (ISO 845).

The rigid foam (i.e. before crushing) prepared has a substantial amountof open cells. Preferably the cells of the rigid foam are predominantlyopen. The crushing may be conducted in any known manner and by any knownmeans. The crushing may for instance be conducted by applying mechanicalforce onto the foam by means of a flat or pre-shaped surface or byapplying variations of external pressure.

In most cases a mechanical force sufficient to decrease the dimension ofthe foam in the direction of the crushing by 1-90%, preferably by 50-90%will be appropriate. If desired crushing may be repeated and/or carriedout in different directions of the foam. Due to the crushing the ballrebound increases considerably in the direction of the crushing. Due tothe crushing the density of the foam may increase. In most cases thisincrease will not exceed 30% of the density before crushing.

The foam may be crushed in the direction of foam rise. A special foam isobtained when the crushing is conducted in a direction perpendicular tothe direction of foam rise : then a foam is obtained with a highlyanisotropic cell structure.

Although it is difficult to give more precise directions for thecrushing since it will inter alia depend on the density of the foam, therigidity of the foam, the type of crushing device used, we believe thoseskilled in the art are sufficiently aware of the phenomenon of crushingof polyurethane foams that they will be able to determine theappropriate crushing manner and means with the above guidance, certainlyin the light of the following examples.

After the crushing the foam may be subjected to a heat treatment inorder to reduce the density increase caused by the crushing. This heattreatment is conducted at 70-200° C. and preferably at 90-180° C. for0.5 minute to 8 hours and preferably for 1 minute to 4 hours.

By crushing the ball rebound is increased at least in the direction ofcrushing. The increase is at least 10%. After the crushing andoptionally the heating a novel flexible foam is obtained which hasexceptional properties. Despite the fact that the foam is flexible, itdoes not show a significant change of the Young's storage modulus E′over a temperature range from −100° C. to +25° C., as described before.The oxygen index of the foam prepared from aromatic polyisocyanatespreferably is above 20 (ASTM 2863). Further it shows a Young's storagemodulus at 25° C. of at most 500 kPa, preferably at most 350 kPa, mostpreferably between 10-200 kPa and a sag factor (CLD 65/25, ISO 3386/1)of at least 2.0, preferably at least 3.5 and most preferably of 4.5-10.CLD hysteresis loss values for the foams are below 55% and preferablybelow 50% (which is calculated by the formula${\frac{\left( {A - B} \right)}{A} \times 100\%},$

wherein A and B stand for the area under the stress/strain curve of theloading (A) and unloading (B) as measured according to ISO 3386/1).Still further these foams can be manufactured with a very low or evennegative Poisson's ratio as determined by lateral extension studiesunder compression of the foams. Finally compression set values of thefoams are generally low, preferably below 40% (ISO 1856 Method A, normalprocedure).

If the Tg^(h) is not too high the foam might be used in thermoformingprocesses to prepare shaped articles. Preferably the Tg^(h) of the foamis between 80 and 180° C., most preferably between 80° C. and 160° C.for such thermoforming applications. Further it was found that foams,which have been made by using a relatively low amount of the polyolshaving a low molecular weight, show a small or non-visible Tg^(h) (themodulus change at Tg^(h) is small or the modulus changes gradually untilthe foam thermally decomposes)by DMTA; such foams may be used forthermoforming activities as well.

Further the foams show good load-bearing properties like compressionhardness values without the use of external fillers together with a goodresilience, tear strength and durability (fatigue resistance) even atvery low densities. In conventional flexible foams often high amounts offiller need to be used to obtain satisfactory load-bearing properties.Such high amounts of fillers hamper the processing due to a viscosityincrease.

The foams of the present invention may be used as cushioning material infurniture and automotive and aircraft seating and in mattresses, ascarpet backing, as hydrophilic foam in diapers, as packaging foam, asfoams for sound insulation in automotive applications and for vibrationisolation in general. The foam according to the present inventionfurther may be used together with other, conventional flexible foams toform composites, like e.g. in mouldings; such composites may also bemade by allowing the ingredients for making the conventional flexiblefoam to form said foam in a mould in the presence of the foam accordingto the present invention or alternatively by allowing the ingredientsfor making the rigid foam according to the present invention to formsaid rigid foam in a mould in the presence of the conventional flexiblefoam followed by crushing the moulding so obtained. Further the foamsaccording to the present invention may be used as textile cover, ascover for other type of sheets, as carpet underlay or felt-replacement;the so-called flame lamination technique may be applied to adhere thefoam to the textile, the carpet or the other sheet. In this respect itis important to note that the foam according to the present invention issuitable to be cut in sheets of limited thickness, e.g. of about 1 cmand less. Still further the foam according to the present invention maybe used as insulation material around pipes and containers.

The invention is illustrated by the following examples.

EXAMPLE 1

(Comparative)

A polyisocyanate mixture was prepared by mixing 56.6 parts by weight ofpolymeric MDI having an NCO value of 30.7% by weight and an isocyanatefunctionality of 2.7 and 43.4 parts by weight of a uretonimine modifiedMDI having an NCO value of 31% by weight, an isocyanate functionality of2.09, a uretonimine content of 17% by weight and 2,4′-MDI content of 20%by weight. An isocyanate-reactive composition was prepared by mixing32.2 parts by weight (pbw) of polyethylene glycol having a molecularweight of 200, 4.5 pbw of ethylene glycol, 42.6 pbw of an EO/PO polyolhaving a nominal functionality of 2, diethylene glycol as initiator, anEO content (except the initiator) of 20.2% by weight (all tipped) and ahydroxyl value of 30 mg KOH/g, 5.5 pbw of diethanolamine, 14.5 pbw ofwater and 0.7 pbw of di-butyl-tin-dilaurate. This composition was anemulsion. 106.1 pbw of the polyisocyanate mixture and 46.9 pbw of theisocyanate-reactive composition (isocyanate index 75.5) were mixed for13 seconds using a Heidolph ™ mechanical mixer at a speed of 5000 roundsper minute (rpm). After mixing the reaction mixture was poured in anopen 5 liter bucket and allowed to react. Prior to the pouring of thereaction mixture into the bucket, the inner walls of the bucket weregreased with release agent Desmotrol™ D-10RT. 2½ minutes after the foamhas stopped rising (foam rise time 70 seconds) the foam was taken out ofthe bucket and allowed to cool to ambient temperature. A rigidpolyurethane foam was obtained. Core foam samples were then cut out ofthe centre of the foam for property evaluation. The core density was 11kg/m³ (ISO 845). When this experiment was repeated on a Komet highpressure, multiple stream dispensing machine using in total 3kg ofmaterial the rigid foam showed excessive thermal degradation.

EXAMPLE 2

(Comparative)

Three isocyanate reactive blends (blend A, B and C) were prepared. BlendA was prepared by mixing 200 pbw of the EO/PO polyol of example 1 and6.5 pbw of ‘DABCO’ T9 (catalyst from AIR PRODUCTS, DABCO is a trademark). Blend B was prepared by mixing 75.5 pbw of polyethylene glycolwith a molecular weight of 200 and 5.56 pbw of ‘IRGANOX’ 5057 (asubstituted diphenyl amine anti-oxydant from Ciba-Geigy Ltd., IRGANOX isa trademark). Blend C was prepared by mixing 23.5 pbw of triethyleneglycol, 40.0 pbw of water and 0.6 pbw of monobasic sodium phosphate.166.1 g of blend A, 65.2 g of blend B, 51.6 g of blend C and 617.1 g ofthe isocyanate blend of example 1 (isocyanate index 100) were mixed for13 seconds using an ‘Ytron’ (trademark) mechanical mixer at a speed of3500 rpm. After mixing the reaction mixture was poured in an open50×50×30 cm³ wooden mould. Prior to pouring the mixture in the woodenmould, the inner walls were covered with paper. One hour after the foamhad stopped rising (foam rise time 70 seconds) the foam was taken out ofthe mould and allowed to cool to ambient temperature. The rigid foam wascut as in example 1. The core density was 13 kg/m³ (ISO 845). The rigidfoam showed no visable discoloration and the amount of extractables was7.3% by weight. This experiment was repeated on a Komet high pressure,four stream dispensing machine with a slightly different isocyanateblend but for the rest the same. To that aim four blends called blend D,E, F and G were prepared. Blend D was prepared by mixing 58.2 kg of theEO/PO polyol of example 1 and 1.88 kg of IRGANOX 5057. Blend E wasprepared by mixing 6792 g of the EO/PO polyol of example 1 and 2208 g ofDABCO T9. Blend F was prepared by mixing 4868 g of polyethylene glycolwith a molecular weight of 200, 1515 g of triethylene glycol, 2579 g ofwater and 39 g of monobasic sodium phosphate. Blend G was prepared bymixing 60.0 kg of the polymeric MDI of example 1 and 51.9 kg of theuretonimine modified isocyanate of example 1. The dispenser was set suchthat stream D, E, F and G were mixed in weight ratios of 18.56 to 2.65to 13.96 to 76.70, respectively, and 3 kg of foam was prepared in anopen, paper lined 50×100×30cm³ wooden mould. The isocyanate indexamounted to 100. The rigid foam had a core density of 13 kg/m³ (ISO 845)and an amount of extractables of 12.4% by weight. Furthermore the coreof the foam showed some discoloration.

Determination of Extractables of a Foam

The amount of extractables is determined by a continuous extractionusing a soxlet apparatus and methanol as a solvent. The equipmentconsists of a 500 ml pear-shaped flask, the soxlet apparatus andaDimroth cooler. A foam sample of 3 to 4 g is cut into pieces ofapproximately 0.3 cm³, brought into an extraction thimble and mounted inthe soxlet apparatus. The extraction is performed with 300 ml methanol.The methanol in the flask is heated by means of an oilbath which is setat a temperature of 140° C. After refluxing for 3 hours, the methanol isremoved from the filtrate by using a rotavapor. Subsequently the weightof the residue in the flask is determined. The amount of extractables isexpressed as weight % calculated from the amount of extracted materialand the weight of the extracted foam sample.

EXAMPLE 3

(Comparative)

Two isocyanate reactive blends (blend A and B) were prepared. Blend Awas prepared by mixing 30 pbw of the EO/PO polyol of example 1, 0.3 pbwof ‘DABCO’ T9 and 0.3 pbw of 1-methyl-1-oxo-phospholene (a carbodiimidecatalyst from Hoechst). Blend B was prepared by mixing 11.3 pbw ofpolyethylene glycol with a molecular weight of 200, 1.95 pbw ofdiethanolamine, 1.58 pbw of ethylene glycol and 4.5 pbw of water. 26.9 gof blend A, 17.3 g of blend B and 108.6 g of the isocyanate blend ofexample 1 (isocyanate index 123) were mixed for 13 seconds with a‘Heidolph’ mechanical mixer at a speed of 5000 rpm. After mixing thereaction mixture was poured in an open 5 liter bucket and allowed toreact. One hour after the foam has stopped rising (foam rise time 70seconds) the foam was taken out of the bucket and allowed to cool toambient temperature. A rigid polyurethane foam was obtained with a coredensity of 16 kg/m³ (ISO 845). Attenuated total reflection Fouriertransform infra red analysis showed the presence of carbodiimide groups(signal at 2140 cm⁻¹).

The core of the foam did not show signs of visible discoloration. Whenthis experiment was repeated with 1.3 kg of material using the YTRONmixer and mixing conditions and the paper lined wooden mould dimensionsof 50×50×30 cm³ of example 2 a rigid foam with a core density of 13.8kg/m³ was obtained which foam showed visible discoloration in the centreof the bun.

EXAMPLE 4

In this example blend D from example 2 was substituted for blend H whichwas prepared by mixing 58.2 kg of the EO/PO polyol of example 1 and 1.88kg IRGANOX 1010 (a sterically hindered phenol antioxidant fromCiba-Geigy Ltd., IRGANOX is a trade name). The dispenser was set suchthat stream H, E, F and G were mixed in weight ratios of 18.56 to 2.65to 13.96 to 76.70, respectively, and 3 kg of foam was prepared in anopen, paper lined 50×100×30 cm³ wooden mould. The isocyanate indexamounted to 100. The rigid foam had a core density of 12.7 kg/m³ (ISO845) and an amount of extractables of 11.6% by weight. The core of thefoams showed no discoloration. The weight ratio of stream G wasincreased to 78.2, 79.8 and 81.3 to produce foams with an isocyanateindex of 102, 104 and 106 respectively. The rigid foams had a coredensity of 13.3, 12.3 and 13.4 kg/m³, respectively (ISO 845) and theamount of extractables amounted to 7.4, 1.5 and 3.4 weight %respectively. None of these foams showed discoloration. The foams withan isocyanate index of 102, 104 and 106 were crushed by one compression(70% CLD) at 100 mm/min in the rise direction, followed by 15 crushings(70% CLD of the height after the first compression) at a rate of 500mm/min in the rise direction of the foam using an INSTRON (INSTRON is atrade mark) mechanical tester mounted with flat plates. After crushing aflexible foam was obtained having no major glass-rubber transitionbetween −100° C. and +25° C. and having the following properties:

isocyanate index 102 104 106 core density after crushing (ISO 845,kg/m³) 14.7 13.3 16.8 Young's storage modulus ratio(E′_(−100°C.)/E_(+25°C.)) 2.7 2.5 2.5 (ISO/DIS 6721-5) Young's storagemodulus at 25° C. (kPa) 215 166 192 (ISO/DIS 6721-5) benzene content, %by weight (calculated) 43.4 44.1 45.2 ball rebound (%, ISO 8307) 53 5553 CLD-40% (kPa, ISO 3386/1) 5.5 5.6 7.5 SAG factor (CLD 65/25, ISO3386/1) 5.7 4.8 8.6

What is claimed is:
 1. A polyol composition comprising, relative to thetotal weight of components (A), (B) and (C); (A) 15-40 parts by weightof a polyether polyol (2) having an average equivalent weight of 70-300,an average nominal hydroxyl functionality of from 2 to 6 and anoxyethylene content of at least 75% by weight, (B) 45-75 parts by weightof a polyether polyol (3) having an average equivalent weight of1000-3000, an average hydroxyl functionality of 2-3, a hydroxyl numberof from 10 to less than 150 mg KOH/g and is represented by the followingstructure:HO—(EO)_(x)—(PO)_(z)—(EO)_(y)—X[—0—(EO)_(y)—(PO)_(z)—(EO)_(x)H]_(n) wherein EO represents an ethylene oxide radical, PO represents apropylene oxide radical, x represents a number from 1 to 15, yrepresents a number from 0 to 6, z represents a value so as to arrive atthe above equivalent weight, n is 1-2 and X is a hydrocarbon radicalhaving 2-10 carbon atoms or a radical represented by the formula—CH₂—CH₂—(O—CH₂—CH₂)₁₋₂—; and (C) 5-20 parts by weight water with theproviso that the composition does not comprise compounds having primary,secondary or tertiary nitrogen atoms.
 2. The polyol compositionaccording to claim 1, wherein polyol (2) has an average equivalentweight of 70-150 and an average nominal hydroxyl functionality of from 2to
 3. 3. The polyol composition according to claim 1 wherein the nominalhydroxyl functionality is 2, x=3-10, y=1-4, n=1 and X is a hydrocarbonradical having 2-6 carbon atoms or a radical having the formula—CH₂—CH₂—(O—CH₂—CH₂)₁₋₂—.
 4. The polyol composition according to claim 2wherein the nominal hydroxyl functionality is 2, x=3-10, y−1=4, n=1 andX is a hydrocarbon radical having 2-6 carbon atoms or a radical havingthe formula —CH₂—CH₂—(O—CH₂—CH₂)₁₋₂—.
 5. The polyol compositionaccording to claim 1 wherein a catalyst enhancing the formation ofurethane and/or urea groups is present in an amount of 0.1 to 5% byweight calculated on the weight of all ingredients used to make thefoam.
 6. The polyol composition according to claim 5 wherein stannousoctoate is present as catalyst in an amount of 0.1 to 3% by weightcalculated on the weight of all ingredients used to make the foam. 7.The polyol composition according to claim 2 wherein a catalyst enhancingthe formation of urethane and/or urea groups is present in an amount of0.1 to 5% by weight calculated on the weight of all ingredients used tomake the foam.
 8. The polyol composition according to claim 7 whereinstannous octoate is present as catalyst in an amount of 0.1 to 3% byweight calculated on the weight of all ingredients used to make thefoam.
 9. The polyol composition according to claim 1 wherein a catalystenhancing the formation of urethane and/or urea groups is present in anamount of 0.1 to 5% by weight calculated on the weight of allingredients used to make the foam.
 10. The polyol composition accordingto claim 9 wherein stannous octoate is present as catalyst in an amountof 0.1 to 3% by weight calculated on the weight of all ingredients usedto make the foam.
 11. The polyol composition according to claim 2wherein a catalyst enhancing the formation of urethane and/or ureagroups is present in an amount of 0.1 to 5% by weight calculated on theweight of all ingredients used to make the foam.
 12. The polyolcomposition according to claim 11 wherein stannous octoate is present ascatalyst in an amount of 0.1 to 3% by weight calculated on the weight ofall ingredients used to make the foam.
 13. The polyol compositionaccording to claim 4 wherein a catalyst enhancing the formation ofurethane and/or urea groups is present in an amount of 0.1 to 5% byweight calculated on the weight of all ingredients used to make thefoam.
 14. The polyol composition according to claim 13 wherein stannousoctoate is present as catalyst in an amount of 0.1 to 3% by weightcalculated on the weight of all ingredients used to make the foam.